US4639347A - Process of making crimped, annealed polyester filaments - Google Patents

Process of making crimped, annealed polyester filaments Download PDF

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Publication number
US4639347A
US4639347A US06/590,291 US59029184A US4639347A US 4639347 A US4639347 A US 4639347A US 59029184 A US59029184 A US 59029184A US 4639347 A US4639347 A US 4639347A
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filaments
steam
crimped
properties
annealed
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Jack A. Hancock
Walter D. Johnson
Alan D. Kennedy
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EIDP Inc
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EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US06/590,291 priority Critical patent/US4639347A/en
Priority to BR8402035A priority patent/BR8402035A/pt
Priority to IN285/CAL/84A priority patent/IN163524B/en
Priority to IE1082/84A priority patent/IE55981B1/en
Priority to FI841725A priority patent/FI80079C/fi
Priority to AU27577/84A priority patent/AU578021B2/en
Priority to EP84302988A priority patent/EP0125112B1/en
Priority to DK220884A priority patent/DK220884A/da
Priority to ES532133A priority patent/ES532133A0/es
Priority to NO841772A priority patent/NO166336C/no
Priority to AT84302988T priority patent/ATE49243T1/de
Priority to DE8484302988T priority patent/DE3480941D1/de
Priority to CA000453503A priority patent/CA1250414A/en
Priority to GR74583A priority patent/GR82071B/el
Priority to MX201249A priority patent/MX159169A/es
Priority to KR1019840002445A priority patent/KR870001252B1/ko
Priority to TR3291/84A priority patent/TR22997A/xx
Priority to PT78550A priority patent/PT78550B/pt
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY WILMINGTON, DE A CORP OF DE reassignment E. I. DU PONT DE NEMOURS AND COMPANY WILMINGTON, DE A CORP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HANCOCK, JACK A., JOHNSON, WALTER D., KENNEDY, ALAN D.
Priority to US06/942,714 priority patent/US4704329A/en
Publication of US4639347A publication Critical patent/US4639347A/en
Application granted granted Critical
Priority to IN215/CAL/88A priority patent/IN168516B/en
Priority to JP1230585A priority patent/JPH02127536A/ja
Priority to SG126/90A priority patent/SG12690G/en
Priority to HK615/91A priority patent/HK61591A/xx
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/20—Combinations of two or more of the above-mentioned operations or devices; After-treatments for fixing crimp or curl
    • D02G1/205—After-treatments for fixing crimp or curl

Definitions

  • This invention relates to a process for annealing drawn polyester filaments which provides products having a novel fine structure and improved balance of filament properties including dyeability, strength, dimensional heat stability, crimp, and low surface cyclic trimer. More particularly it relates to a process for annealing drawn polyester filaments while under restraint prior to being crimped and improved products which result therefrom.
  • U.S. Pat. No. 3,816,486 to Vail discloses a two-stage drawing process for poly(ethylene terephthalate) filaments which can be followed by relaxation or annealing. Disclosed annealing temperatures range from 180°-240° C. Art such as this generally does not recognize any criticality associated with the manner for heating the filaments with regard to the resulting annealed filament properties. The presently preferred heating method for annealing drawn filaments in commercial polyester staple production is the use of heated metal rolls.
  • U.S. Pat. No. 3,452,132 to Pitzl discloses a process for simultaneously drawing and annealing polyester textile yarn wherein steam is jetted on the filaments in an enclosure with sufficient velocity to open the bundle and to raise the temperature of the filaments substantially instantaneously to at least above their second order transition temperature and thereby initiate drawing with simultaneous annealing.
  • Steam at superatmospheric pressure is used as the fluid for the high velocity jet because of the effectiveness of the condensing steam as a heat transfer agent.
  • the steam pressure is said not to be critical and no benefits are indicated for increasing the yarn temperature to above about 180° C.
  • Such a process is not compatible for drawing and annealing large bundles of filaments such as employed for tows in the manufacture of polyester staple.
  • An object of this invention is a process for annealing a tow of drawn filaments of poly(ethylene terephthalate) to provide an improved balance of filament properties including strength, dyeability, and shrinkage, and/or crimpability, and/or low surface cyclic trimer deposits. Another object is the improved products made thereby. Still another object of the invention is annealed crimped filaments of poly(ethylene terephthalate) having a novel unexpected combination of fine structure and improved filament properties.
  • saturated steam maintained at a pressure of at least about 150 psig can be used to anneal drawn filaments of poly(ethylene terephthalate) while under tension and prior to being crimped with unexpectedly beneficial results.
  • the steam-annealed crimped filaments have been found to have a superior overall balance of properties which is usually accompanied by an unexpectedly different fine structure.
  • crimped filament is used generically to embrace not only continuous filaments, generally in the form of a tow, but also staple fiber, and products thereof. It is, however, genearlly easier to measure the parameters mentioned herein for continuous filaments, rather than for staple fiber.
  • this invention provides a process for manufacturing crimped, annealed filaments of poly(ethylene terephthalate) comprising advancing a tow of the filaments, which have been substantially fully drawn, through a pressurized zone of steam maintained at a pressure of at least about 150 psig for at least about 0.2 sec., and preferably for a time sufficient to heat substantially all of said filaments up to at least the steam saturation temperature corresponding to the steam pressure, while controlling filament length within the range of from about 5% extension to 10% retraction, withdrawing the tow of filaments from the zone into ambient atmospheric pressure whereupon they become rapidly cooled by vaporization of water to a temperature of about 100° C.
  • the anneal filaments of this invention can be crimped in a conventional manner as in a stuffer-box crimper, as taught for example in U.S. Pat. No. 2,311,174 to Hitt, and then dried and relaxed at a temperature of less than about 125° C., since too high a temperature can destroy the benefits of the invention.
  • the filaments of this invention consist essentially of poly(ethylene terephthalate), that is polymer in which at least about 93% (by weight as used herein) of the repeating radicals consist of the dioxyethylene and terephthaloyl radicals.
  • the remaining radicals can consist of ionic or neutral (free of ionic dye sites) co-monomer radicals including radicals such as 5-sodium-sulfoisophthaloyl, dioxydiethylene ether, i.e., the derivative of diethylene glycol (DEG), glutaryl, such as derived from dimethyl glutarate (DMG), and the derivative of poly(ethylene oxide), such as PEO having a molecular weight of 600.
  • radicals can also include those from (including their mixtures) 4-9 carbon straight-chain aliphatic diacids, especially glutaryl and adipyl, and of glycols including diethylene, triethylene and tetraethylene glycol, of 400-4000 molecular weight poly(ethylene glycol), tetramethylene and hexamethylene glycol, poly(butylene glycol) of 400-4000 molecular weight, and copolyethers of ethylene/propylene and ethylene/butylene glycols of 400-4000 molecular weight.
  • glycols including diethylene, triethylene and tetraethylene glycol, of 400-4000 molecular weight poly(ethylene glycol), tetramethylene and hexamethylene glycol, poly(butylene glycol) of 400-4000 molecular weight, and copolyethers of ethylene/propylene and ethylene/butylene glycols of 400-4000 molecular weight.
  • the novel filaments of the invention are characterized by an overall balance of properties that is superior, i.e. improved over comparable hot rolled filaments, the degree and nature of this improvement, that is achieved by the steam-annealing process, varies depending upon the chemical constitution of the particular polyester involved.
  • the improved filaments have a T 7 of at least about 1.5 gpd, a T+T 7 of at least about 7 and generally less than about 10 gpd, along with a dry heat shrinkage (196° C.) of less than 10%.
  • Such filaments of the invention have a dyeability/orientation balance characterized by a "D" number of less than about 3.8 and greater than about 1.8 and a trimer “T” number that is preferably less than about 20.
  • "D" number and trimer “T” number are as defined hereinafter and are derived from conventionally measured properties.
  • filaments of the invention can be grouped according to their intended use. Where strength is of primary concern the filaments are of a polymer containing at least 97% by weight of dioxyethylene and terephthaloyl radicals. Any remaining radicals are preferably selected from the group consisting of glutaryl, oxy-poly(ethylene oxide) and dioxydiethyleneoxide. A small amount of ionic radical (up to about 0.3% 5-sodium-sulfoisophthalate) may be optionally present.
  • a preferred group of strong filaments is of polymers having at least 97% dioxyethylene and terephthaloyl radicals, substantially free of ionic dye sites, which in addition to the above balance of properties have a crystalline fine structure within the area HIJK in FIG. 2, or in areas LMNOP or NOPQR of FIG. 3.
  • the filaments are of a polymer containing at least about 3% and not more than about 7% by weight of neutral (i.e., substantially free of ionic dye site) organic polyester radicals, particularly those selected from the group consisting of (or derived from) diethylene glycol, glutarate, adipate, and poly(ethylene oxides) having a molecular weight of less than about 4000.
  • Filaments of such copolymers of the invention have the improved balance of properties as defined by a T 7 of at least about 1.1, a T+T 7 of at least about 5 and preferably less than about 7 gpd, a dry heat shrinkage (at 196° C.) or less than 10%, a "D" number of less than 3.8 and greater than about 1.8, a trimer "T” number preferably of less than about 20 and dye rate (RDDR) of at least 0.12.
  • Such copolymer filaments are preferably annealed while allowing a retraction in filament length (difference in feed and puller roll speeds) within the range of about 3 to 10%.
  • Such filaments include ones having a superior combination of pilling resistance, ease of dyeability, tensile properties and heat stability relative to present commercial copolymer filaments.
  • Improved ionically-modified cationically dyeable filaments of the invention contain at least 93% dioxyethylene and terephthaloyl radicals, at least 1.3% 5-sodium-sulfoisophthaloyl radicals and from 0 to about 4% (including DEG impurity) of other neutral radicals as defined above.
  • Such filaments have a T 7 of at least about 1.2 gpd, a T+T 7 of at least about 5 gpd and "D" and trimer "T” numbers as for the above polymers.
  • Preferred 93-97% copolymers and ionic terpolymers have a crystalline fine structure wherein the area STUV of FIG. 4.
  • FIG. 1 schematically shows an apparatus suitable for and an anneal/crimp process of the invention.
  • FIGS. 2-4 are graphs showing X-ray fine structure details of Long Period Spacing, Apparent Crystallite Size and Percent Crystallinity for steam-annealed filaments of the invention.
  • FIG. 5 shows graphs plotting tensile properties and surface trimer against relative viscosity.
  • This invention can provide filaments with unexpectedly superior tensile-dye-shrinkage properties, and which usually are combined with improved crimpability and lower surface cyclic trimer content.
  • the crimped tow is straightened by application of about 0.1 gpd load and 0.5 gm clips 66.6 cm apart are attached to the extended tow. The tow is then cut 11.2 cm beyond each clip to give a sample of 90 cm extended length. The sample is suspended vertically, hanging freely from one of the clips to allow retraction to crimped length. After about 30 seconds, clip-to-clip distance is measured. ##EQU1## where L c is clip-to-clip distance in the free-hanging state. Tow denier is calculated from weight of the 90 cm extended length sample. Average denier per filament is calculated from tow denier and the number of filaments in the tow.
  • Tenacity at break elongation (T), and tenacity at 7% elongation (T 7 ) are determined from the stress-strain curve in a conventional manner using an "Instron" machine with a sample length of 10 inches (25 cm) and a rate of sample elongation of 60% per minute, at about 75° F. (24° C.)/65% RH. They are given throughout in gpd units.
  • Flex life is measured by repeatedly bending single filaments, each tensioned to 0.3 gpd, through an angle of 180° over a wire of diameter 0.001 inch (0.025 mm). If the denier exceeds 5 dpf, the diameter should be 0.003 inch (0.075 mm). Twenty-two filaments are flexed simultaneously. Flex life is defined as number of cycles at the time the eleventh filament fails. This test is repeated, i.e., at least two bundles of filaments are tested, and the average number of cycles is taken as the flex life.
  • Residual shrinkage is preferably and most accurately measured on uncut, crimped dried tow.
  • the ends of a bundle of filaments of about 250 denier are tied to form a loop about 30 cm long.
  • a load of about 0.1 gpd is applied to straighten crimp and loop length is determined to the nearest mm.
  • the loop is coiled and freely suspended with no tension in a 196° C. forced air oven for 30 minutes. After cooling, length is remeasured as before. ##EQU2## where L and F are initial and final loop lengths, respectively.
  • a single fiber or bundle of about 25 fibers is mounted between a fixed clamp and a movable clamp attached to a Vernier scale. Sufficient tension is applied to straighten crimp and extended length is measured. The moveable clamp is adjusted to release tension and allow fibers to shrink freely. The assembly is transferred to a 196° C. force air oven for 30 minutes. After cooling, extended fiber length is remeasured and shrinkage calculated as above.
  • Boil-off-shrinkage is measured as in Piazza and Reese (U.S. Pat. No. 3,772,872).
  • Density is the preferred basis for calculating percent crystallinity for homopolymers. After correcting for any delusterant content, the percent crystallinity is calculated on the basis of an amorphous density of 1.335 gm/cc and a crystalline density of 1.455 gm/cc for 100% homopolymers. However, as the amount of modifier increases, the amorphous and crystalline densities of copolymers can differ significantly from these values conventionally used for homopolymers, so calculation of percent crystallinity on this basis can be misleading. This is especially true when the copolymer contains more than 3% of modifier, but depends on the particular modifier. Percent crystallinity of such copolymers should be calculated from the Crystallinity Index (CI) using the equation:
  • Melting point is defined as the temperature of the melting endotherm peak measured in a N 2 atmosphere using a Du Pont 1090 Thermal Analyzer with a Du Pont 1910 scanning calorimeter attachment. Sample size was 5 ⁇ 0.2 mg and scanning rate was 20° C. per minute.
  • the meridional small-angle X-ray long-period peak was measured using a Kratky Small-Angle X-Ray Camera (made by Anton Paar K. G., Graz-Strassgang, Austria, and sold by Siemens Corp., Iselin, N.J.).
  • the radiation was CuK ⁇ (copper K-alpha) emitted by an X-ray tube (Siemens AG Cu 4SK-T) having a 2.5 ⁇ 7 mm focal spot and especially designed to be used with the Kratky Camera.
  • the radiation was filtered by a 0.7 ml (18 microns) Ni foil to remove CuK ⁇ radiation and detected by a NaI(Tl) scintillation counter employing single-channel pulse-height-analysis set to pass 90% of the CuK ⁇ radiation symmetrically.
  • the pulse-height analysis removes the major portion of the continuous radiation emitted by the X-ray tube.
  • the specimens were prepared by winding uncut, crimped tow on a 2.5 cm square frame with an opening sufficient to pass the X-ray beam.
  • the tow was wound with sufficient tension to yield a uniform thickness of essentially parallel fibers. If the measurement is to be on cut staple fibers, these can be spun into a yarn to maximize fiber parallelization. Care must be taken in yarn preparation to avoid mechanical damage such as cold draw which might change the fiber structure.
  • appropriate control samples tested both as uncut tow and as a spun staple yarn should be run to determine any correction factors needed to normalize spun yarn data to that of uncut tow.
  • the wound specimen is mounted in the Kratky camera so that the fibers are vertical (the fiber axis is coincident with the diffraction vector, which bisects the incident and the diffracted beams).
  • the Kratky camera scans in a vertical plane about the horizontal axis described by the intersection of the X-ray beam and the sample.
  • the sample is scanned between 0.1° and 2.0° 2 ⁇ in 0.025° steps.
  • Data are digitized for computer analysis and a smoothed curve is constructed using a running fit to a second order polynomial.
  • the instrument background is removed by subtracting, point-by-point, a background scan obtained with no sample multiplied by the observed transmission, T.
  • a correction factor, C is determined from the transmission, T, as: ##EQU3##
  • the data are then corrected by multiplying each point by C, which corrects for the amount of sample in the X-ray beam and puts data from every sample on an equivalent basis. If experiments cover an extended period of time, one sample should be retained as a reference and scanned as necessary to monitor any drift in instrumental response.
  • Measured long-period spacing sometimes depends on the experimental method.
  • a photographic-film-based procedure can give a slightly different result from the goniometer procedure described above.
  • Spun filaments are prepared from 21 RV polyethylene terephthalate homopolymer containing about one weight percent or less of impurities such as diethylene glycol. Filaments are air quenched and spun at about 1500 ypm (1372 meters/min) to 4 dpf. The spun filaments are two-stage drawn in an aqueous environment in a process basically similar to that described by Vail (U.S. Pat. No. 3,816,486) and then annealed at constant length over heated rolls. Draw ratios may differ somewhat from Vail and are selected to ensure uniform draw in the first stage and a final tenacity of about 6.3 gpd. A second stage draw ratio of about 1.15 is suitable.
  • Annealing rolls are heated to first dry the filaments and then heat them to a temperature of 177° C. for about 1.5 seconds.
  • Annealed filaments are water-quenched then stuffer box-crimped and dried in air under zero tension at 120° C. for 10 minutes. Filaments are spread into a thin ribbon on the anneal rolls for maximum filament to filament heat treatment uniformity. These filaments have an LPS of 120 ⁇ when tested as described above.
  • Apparent crystallite size is measured as described by Blades (U.S. Pat. No. 3,869,429 Col. 12) with some modifications.
  • High intensity X-ray source is a Phillips XRG-3100 with a long, fine focus copper tube. Diffraction is analyzed with a Phillips single axis goniometer equipped with a theta-compensating slit and a quartz monochromator set to exclude copper K ⁇ radiation. Diffracted radiation is collected in step scanning mode in 0.025° steps with a 1.5 second per step count time. The digital data so collected are analyzed by a computer and smoothed by a running fit to a second order polynomial.
  • Crystalline polyethylene terephthalate filaments show a clear 010 diffraction peak with a maximum at about 18° and a minimum at about 20°.
  • the computer is programmed to determine positions of the maximum and minimum from the second derivative of the polynomial, to define the base line as a straight line which begins at the minimum at about 20° and joins the diffractogram tangentially at 10° to 14°, to determine peak width at half height, to correct for the instrumental contribution to line broadening and to calculate ACS as described by Blades.
  • Crystallinity Index is determined from the same diffractogram as ACS.
  • the computer is programmed to define a straight base line which joins the diffractogram tangentially at about 11° and 34°.
  • Crystallinity index is defined as (A ⁇ 100)/(A-B) where A is the intensity of the 18° 010 peak above this base line and B is the intensity of the 20° minimum above this base line.
  • Relative Viscosity is the ratio of the viscosity of a 4.47 weight on weight percent solution of the polymer in hexafluoroisopropanol containing 100 ppm sulfuric acid to the viscosity of the solvent at 25° C.
  • DDR (disperse dye rate) is measured as described by Frankfort and Knox (U.S. Pat. No. 4,195,051, Col. 13).
  • RDDR is calculated from DDR by normalizing to the surface-to-volume ratio of a 1.50 dpf round fiber.
  • correction may also be made for denier increase caused by shrinkage in the dye bath (i.e., boil-off shrinkage, or BOS).
  • BOS boil-off shrinkage
  • fibers of the invention have low BOS and such correction is usually negligible.
  • trimer concentration is determined by conventional UV spectrophotometry based on absorbance at 2860 ⁇ . Correction for interfering impurities, for example, finish ingredients with absorbance at 2860 ⁇ , may be needed.
  • a calibrating standard is prepared by purifying a sample containing trimer by repeated recrystallization from methylene chloride to yield pure trimer melting at 325°-328° C.
  • Trimer level increases with draw ratio and orientation.
  • the word “Trimer” is used generically to cover any low molecular weight polymer on the surface of the filament.
  • compositions in the Examples are based on analysis of the crimped filaments and refer to polymer components other than ethylene terephthalate units.
  • composition is defined as weight % of ethylene-diacid repeat units.
  • DMG dimethyl glutarate comonomer
  • the polymer composition is defined in terms of weight % ethylene glutarate.
  • dialcohol modifiers the composition is specified as grams dialcohol formed by hydrolysis of 100 gm. of copolymer. Unless indicated otherwise, all the polymer compositions in the Examples contained 0.3% by weight of TiO 2 , as delusterant.
  • WMOD is the total weight % "foreign" radicals incorporated in the polymer chains.
  • "Foreign” denotes chemical species other than dioxyethylene and terephthaloyl radicals.
  • the foreign species is --CO--(CH 2 ) 3 --CO--.
  • the total weight % includes dioxydiethylene ether (DEG) links usually formed in the polymerization reaction.
  • DEG dioxydiethylene ether
  • MDR is the machine draw ratio used to make the substantially fully drawn filaments that are fed to the steam-annealing pressurized zone (steam chamber 20 in FIG. 1).
  • PRUD is the ratio of the speed of the puller roll (22), after the steam chamber, to the speed of the draw roll (14), before the steam chamber.
  • the filaments used in the process of the invention may be drawn by any means known to those skilled in the art.
  • a draw process substantially of the type described by Vail (U.S. Pat. No. 3,816,486) is suitable for the drawn filament supply.
  • First and second stage draw ratios are selected based on polymer composition, spun orientation and desired final tensile properties. Single-stage processes are also suitable.
  • filaments should not be overdrawn. Excessive draw ratios yield no advantage in drawn filament tenacity compared to lower draw ratios. However, it has been found that dye rate is adversely affected when draw ratio is excessive.
  • optimum draw ratio depends on polymer composition and relative viscosity. It is known to those skilled in the art that some adjustment can be required to determine optimum draw ratio for any given combination of polymer type and spun orientation.
  • the drawn filament bundle is advanced to, enters and then leaves the steam chamber through orifices sized and designed to maintain the desired superatmospheric pressure inside the chamber.
  • Filament bundle thickness and shape e.g., round or ribbon
  • chamber residence time are adjusted so that substantially all filaments reach the saturated steam temperature.
  • tow bundles of about 50,000 denier circular orifices 0.125 inch (3.2 mm) in diameter and 1.25 inches (32 mm) long are satisfactory.
  • Residence times can be from about 0.2 to about 1 second.
  • a low residence time, such as 0.2 to 0.6 seconds may be preferred when it is desired to minimize surface trimer content, otherwise higher residence times may be preferred.
  • Steam can be fed into the chamber substantially uniformly along its length, as from orifices along a manifold along the inside top of the chamber, thus avoiding impingement of the incoming steam directly onto the filaments as is required in steam-jet drawing.
  • the chamber is fitted with a condensate outlet.
  • the steam supply system is sized and fitted with control valves and gauges as appropriate to maintain and measure pressure inside the chamber. As the tow of filaments leaves the chamber, it is rapidly cooled by evaporation of water to about 100° C., or less, at normal atmospheric pressure.
  • the tow is then forwarded to a crimper.
  • fiber tensile properties, particularly T 7 and crimp frequency and crimp amplitude depend both on temperature of the tow entering the crimper and on temperature inside the crimper. Excessive temperatures can reduce T 7 and give undesirably high crimp frequency. Additional cooling of the tow before the crimper may be needed and temperature inside the crimper must be carefully controlled for optimum results. A suitable lubricating finish is generally applied prior to crimping.
  • the steam pressure in the process of this invention preferably should not exceed about 320 psig (2300 kPa) for the higher melting polymers, corresponding to a saturation temperature of about 220° C.
  • Higher temperatures adversely affect filament properties and create operability problems because of proximity to the filament softening temperature.
  • Copolymers which have a lower softening temperature require a correspondingly lower maximum operating temperature, i.e., a lower steam pressure. It is preferred that the maximum temperature that the filaments reach be that of the condensation temperature corresponding to the steam pressure in the steaming zone. Other than to control flooding, superheating is unnecessary.
  • fibers annealed with saturated steam to similar levels of crystallinity and of shrinkage generally have an LPS of 125-150 ⁇ .
  • Microcrystals would inhibit motion of amorphous chain segments at low temperatures, thereby reducing low temperature shrinkage and making crimping more difficult. However, they would melt at relatively low temperatures and, therefore, not contribute to length stability at high temperatures. Because they reduce amorphous chain mobility, microcrystals could also reduce dyeability.
  • the fine structure of the filaments of the invention and the associated advantages thereof can be most readily detected by measurement of dye rate and filament orientation.
  • Dye rate reflects both mobility and orientation, whereas the sum of the tenacity and T 7 , i.e., T+T 7 , directly reflects orientation alone.
  • the fibers of this invention have an improved combination of properties including improved strength, low dry heat shrinkage to maximize fabric yield after heat-setting, and a high dye rate to reduce dyeing costs.
  • Some filaments of this invention further reflect their improved properties through superior crimp and a lower concentration of surface cyclic trimer. The latter provides improved processability and fewer deposits during processing into yarn.
  • the improved filaments of the invention can be described by their position in a three-dimensional space described by three coordinates relating to amorphous orientation (namely T+T 7 ), amorphous chain mobility (namely RDDR) and weight percent copolymer modifier (i.e. WMOD). This is why we have used herein the "D" number, which is defined above, as a simple function of the above three parameters, and which is less than about 3.8 for strong, low-shrinkage annealed filaments of the invention.
  • a steam-annealed fiber containing 2.9% ethylene glutarate derived from dimethyl glutarate (DMG) was found to be fully equivalent in dye rate to a known fiber containing 5.7% ethylene glutarate, and to have substantially better tensile properties in addition.
  • DMG dimethyl glutarate
  • copolymers show similar improved development of crimp amplitude and reduced levels of surface cyclic trimer as obtained with homopolymers.
  • the steam-annealed filaments of the invention have about a 1.5 ⁇ higher dye rate than roll-annealed filaments made from the same base polymer and of similar orientation, crystallinity and shrinkage.
  • steam-annealed homopolymer filaments have less surface cyclic trimer (SCT) than roll-annealed filaments of comparable shrinkage.
  • SCT surface cyclic trimer
  • the trimer level generally increases with draw ratio, i.e., orientation.
  • Filaments of this invention may be prepared from multifilament tows in textile deniers per filament (dpf), preferably less than 6.0 dpf, as well as in heavier carpet and industrial filament and yarn sizes.
  • the filaments preferably are combined in the form of a heavy tow, such as is greater than about 30,000 denier, and especially greater than about 200,000 denier.
  • the filaments are not restricted to any particular type of filament cross-section and include filaments of cruciform, trilobal, Y-shaped, ribbon, dog bone, scalloped-oval and other non-circular cross-sections, as well as round.
  • the filaments may be used as crimped continuous filaments, yarns, or tows, or as staple fibers of any desired length, including conventional staple lengths of from about 0.75 to about 6 inches (about 20 to 150 mm).
  • the filaments are crimped to the desired degree depending upon their use.
  • the filaments preferably have a crimp index of at least about 20.
  • the invention is illustrated in the following Examples, which illustrate also the results of comparative workings, some without steam and some using saturated steam at pressures lower than about 150 psig, i.e., lower than about 1100 kPa, to demonstrate the different results that have been obtained.
  • the actual pressures were measured. Because of variations in readings from different pressure gauges, and because extremely precise pressure readings have not generally seemed particularly significant with respect to differences in properties of the resulting filaments, the pressures in the Examples have been rounded to the nearest 5 psig.
  • the high saturated steam pressures that are used according to the invention are believed to be important because they enable the filaments, which are generally present in extremely large numbers, to be heated efficiently and rapidly to the temperature of the saturated steam.
  • annealing temperatures have been calculated from Standard Tables, and are also referred to herein, because the precise temperature can be of critical importance.
  • these annealing temperatures are considered, rather than pressures, the improvements that can be obtained by raising the pressure of the saturated steam are with certain polymer compositions, very dramatic in terms of the amount the properties can be changed by a relatively small increase in temperature.
  • Item 9 shows a significantly improved shrinkage of 6% over Item 8 (10%), although the temperature of the saturated steam was only 5° higher (188° instead of 183°), whereas the difference in shrinkage between Items 7 and 8 is smaller (only 2%), despite a rise in temperature of 12°. It will be noted also that the LPS of Item 9 (126 ⁇ ) is significantly larger than those of Items 7 and 8 (114 and 115 ⁇ ).
  • This Example demonstrates superior filaments made by annealing with saturated steam at pressures of at least about 150 psig (above 1100 kPa).
  • tow 11 of drawn filaments is supplied from source 10 by feed rolls 12, 14 aligned with the inlet of the steam chamber 20 and advanced through chamber 20 at a controlled length by adjustable-speed puller rolls 22, 24 aligned with the chamber outlet.
  • the tow is then forwarded to crimper 30 and conventionally crimped.
  • From there crimped tow 11' passes to dryer-relaxer oven 40 where the crimped filaments are conventionally dried in a relaxed state.
  • Pressurized steam is supplied to chamber 20 via manifold 21. Condensed water is removed from chamber 20 by condensate outlet 23. Conventional steam control valves and gauges are not shown.
  • the tension on the filaments during annealing is controlled by rolls outside the steam chamber, and all discussion herein of extension or retraction during annealing or, e.g., in the pressure zone should be understood in this sense.
  • the temperature profile along the filaments may affect the location where the filaments tend to retract. So the annealing may take place in more than one step, with different extensions and/or retractions in these steps. Indeed more than one such annealing step may prove desirable in some instances.
  • Filaments of poly(ethylene terephthalate) homopolymer (0.5% diethylene glycol impurity) of about 21RV, and having 4.0 dpf were spun at 1500 ypm (1372 meters/min) and collected.
  • the resulting tow of 31,500 filaments is drawn in two stages using a process substantially of the type as described in U.S. Pat. No. 3,816,486 (Vail) to a drawn dpf of about 1.5.
  • the tow is passed from the last stage draw rolls through a pressurized steam chamber, while maintained under a controlled length, for 0.4 seconds, withdrawn into ambient atmospheric pressure, accompanied by rapid cooling to about 100° C. while still at said controlled length.
  • the tow is then passed through a 70° C. water-spray with 0.3% finish and then steam-crimped in a conventional manner using a stuffer-box crimper. All crimped fibers were dried at substantially zero tension in a relaxer oven at 90° C. unless specified.
  • the pressurized steam annealing chamber is 15 inches (38 cm) long with an inside diameter of about 1.4 inches (3.6 cm).
  • the tow entrance and exit orifices are 0.125 inch (3.2 mm) diameter and 1.25 inches (3.2 cm) long. Steam enters the chamber horizontally from orifices spaced along sides of a manifold along the inner top of the chamber.
  • Table 1 Properties of filaments made under various conditions are shown in Table 1.
  • Item 1 Table 1, reasonably high orientation fibers can be made by drawing conventionally and with no annealing after cooling the drawn filaments, with a fairly good combination of T+T 7 and dye rate (RDDR), but residual dry heat shrinkage (DHS) is unacceptably high, being greater than 10%.
  • RDDR dye rate
  • DHS residual dry heat shrinkage
  • this shrinkage can be improved by drying the filaments at a higher temperature after crimping but this reduces orientation and dye rate.
  • Items 13 to 15 show different drawing conditions, namely lower draw ratios and more letdown to give lower TDRs than in items 9 to 11.
  • a high steam pressure 200 psig, 1480 kPa
  • a desirably low shrinkage of 6% was obtained, whereas higher shrinkages were obtained for the other items using lower pressures.
  • the shrinkage value of 9%, shown for item 13, is surprisingly low, it has been our experience that steam pressures of the order of 100 psig (about 800 kPa) do not generally give a good balance of properties, and this measurement may have been an aberration.
  • a high steam pressure of about 150 psig (1100 kPa) or even more is generally used to obtain the desirable low shrinkages, which are preferably not more than 8%.
  • the low shrinkage can be obtained by other means, the low shrinkage has not previously been obtained with the desirable balance or properties, as disclosed herein.
  • the shrinkage is significantly affected by temperature.
  • This Example demonstrates filaments of cationically-dyeable copolymers of poly(ethylene terephthalate) of RV about 17 (items 1-1 to 1-6) and about 18 (items 1-7 and 1-8), and containing 0.2% TiO 2 , in Table 3.
  • Steam-annealed Item 1-5 has superior tensile properties and dye rate as compared with unannealed Item 1-1 filament. (It was found to have a 70% higher dye rate than hot-roll annealed filaments of similar orientation, now shown.) Particularly good dye rate is obtained if the fiber is allowed to retract about 10% in the steam annealing step. For instance, Item 1-6 was allowed to retract 12%, and is about equal to Item 1-1 in orientation but has a 1.5-2 ⁇ higher dye rate.
  • Best filament properties require annealing pressures of at least about 150 psig (1100 kPa). Item 1-4 steam-annealed at 95 psig (760 kPa) is significantly worse than Item 1-5, both in residual shrinkage and in dye rate.
  • Steam-annealing of the invention can allow substantial reduction in copolymer content with no sacrifice in dye rate. For example compare Items 1-8 and 1-1.
  • This Example demonstrates filaments of RV of about 20 from poly(ethylene terephthalate) containing glutaryl radicals from dimethyl glutarate (DMG) comonomer and 0.2% TiO 2 , in Table 4.
  • DMG dimethyl glutarate
  • Steam-annealed filament 2-8 is superior to unannealed filament 2-1 in tensiles and in dye rate.
  • Item 2-4 steam annealed at a pressure of about 95 psig (760 kPa) has an unacceptably high dry heat shrinkage of 12 and low LPS demonstrating again the improvement achieved by using higher annealing pressures.
  • This Example compares the effects of saturated steam-annealing at 198° C. (200 psig, 1480 kPa) of a cationically dyeable terpolymer of poly(ethylene terephthalate) made from the dimethyl esters of glutaric and 5-sodium-sulfoisophthalic acids and containing DEG impurity with a commercial fiber.
  • the polymer has an RV of about 17 and 5.8 dpf filaments are spun at 1500 ypm (1372 meters/min) and drawn 2.8 ⁇ using a puller roll underdrive of 0.92 for a total draw ratio of 2.6.
  • the filaments are annealed with saturated steam at 200 psig, crimped in a stuffer-box crimper and dried at 80° C.
  • the filaments have a crimp index of 29.
  • the crimped rope is cut to 1.5 inch (38 mm) staple and spun into yarns which are knitted into fabric.
  • the fabric is dyed without carrier at the boil with disperse and with cationic dyes and compared with dyed 2.25 dpf commercial cationically dyeable polyester staple (Type 64 made by E. I. du Pont de Nemours and Company). Filament tensile properties and dye results are shown in Table 5. It is seen that the dye rate and the dye bath exhaust by the steam-annealed filaments are significantly superior to those of the commercial fiber. It is surprising that higher exhaust is obtained, even with cationic dyes, for the test item of the invention which contained 40% less reactive dye sites than the commercial fiber.
  • a comparison of steam-annealed Item 3-3 with Item 3-1 clearly reflects the advantages of the invention in producing filaments having an improved crimp index, low surface cyclic trimer and high dyeability at otherwise relatively comparable orientation and shrinkage levels.
  • This Example demonstrates in Table 7 annealing according to the invention using different annealer retractions on 3.2 dpf filaments of RV about 21 of poly(ethylene terephthalate) homopolymer (1% DEG impurity) spun at 1900 ypm. All the items M, D and R are seen to have a high dye rate, high crimp index and low cyclic trimer level.
  • This Example demonstrates copolymer filaments of this invention containing poly(ethylene oxide) of 600 molecular weight annealed with steam at 200 psig in Table 8.
  • This Example illustrates the properties and fine structure of steam-annealed fibers containing 97% by weight or more dioxyethylene and terephthaloyl radicals.
  • Table 9 gives properties of samples prepared from the homopolymer spun supply of Example 1, at several draw ratios, anneal retractions and anneal pressures.
  • a representative crimped sample from this series had a melting point of 257.4° C.
  • Item 6 was prepared at a pressure of only 110 psig (860 kPa).
  • Items 1 and 2 in Table 10 were samples of polyethylene terephthalate containing 2.35% DEG, spun at 1500 ypm (1372 meters/min) to filaments of 4.0 dpf, and of about 20 RV, which were drawn, annealed and crimped as described in Example 1.
  • a representative crimped sample had a melting point of 249.6° C.
  • Items 3 to 6 were samples of polyethylene terephthalate containing 2.1% polyethylene oxide of 600 molecular weight, 1.0% DEG and 0.2% TiO 2 spun at 1900 ypm (1737 meters/min) to 3.36 dpf filaments, of about 22 RV, which are drawn, annealed and crimped as described in Example 1.
  • a representative crimped sample had a melting point of 253.1° C.
  • Items 7 to 9 were samples of polyethylene terephthalate containing 3% ethylene glutarate (1.8% glutaryl radicals), 1.2% DEG and 0.2% TiO 2 , spun to 3.2 dpf filaments, of about 20 RV, which were drawn, annealed and crimped as described in Example 1.
  • a representative crimped fiber had a melting point of 246.5° C.
  • FIG. 2 shows relationship between LPS and ACS for items of the invention from Tables 1, 2, 7, 9 and 10.
  • Items in the Tables with ACS and LPS falling below the links HK and KJ were made at anneal temperatures below 185° C. (below 150 psig) and have high residual shrinkages. Further, although high shrinkage fibers usually have relatively high dye rates, those falling outside the area HIJK have the same or a poorer balance of orientation and dye rate than those within the area. This is evident by comparing "D" numbers in the tables.
  • Table 10, Item 2 is an example of an "overdrawn" filament. Despite a favorable crystalline fine structure, its "D" number is high.
  • FIG. 3 shows relationships between the ratio of CS to LPS, and weight % crystallinity calculated from density for items containing 1% or less DEG (Tables 1, 2, 7, 9). Best filaments fall within the area LMNOP.
  • This Example illustrates in Table 11 novel properties and fine structure of filaments of copolymers containing more than 3% by weight of WMOD.
  • Example 3 The spun supply of Example 3 was used to prepare Item 1.
  • a representative crimped sample had a melting point of 242° C.
  • Item 5 was prepared from the spun supply of Item 1-1 of Example 2.
  • a representative sample of crimped tow had a melting point of 247° C.
  • Polyethylene terephthalate of about 22 RV containing 4.6% polyethylene oxide of 600 molecular weight, 0.7% DEG and 0.2% TiO 2 was spun at 1900 ypm (1737 meters/min) to give filaments which were drawn, annealed and crimped at several draw ratios and annealer retractions to give Items 6 to 9.
  • Filaments from the terpolymer spun supply of Example 4 were single-stage drawn, annealed and crimped at several draw ratios, annealer retractions and annealer steam pressures to give the fine structure parameters in Table 12.
  • the LPS coordinates of the area HIJK in FIG. 2 and STUV in FIG. 4 are similar (125 to 150 ⁇ and 124 to 150 ⁇ respectively) but the ACS coordinates for filaments with WMOD 3% are shifted by about 3.5 ⁇ . Presence of comonomer increases ACS significantly but changes LPS only slightly.
  • Item 1 exemplify unexplained inconsistencies; probably normal experimental error.
  • the properties of Item 1 are self-consistent; the LPS/ACS fall out of the preferred area in FIG. 4 and the dry heat shrinkage is unacceptably high.
  • annealing steam pressure was in the preferred range and based on other samples, a fully acceptable filament was expected. It is believed that an error in the experiment was made, however, it is possible that some copolymers may require anneal pressures in excess of the 150 psig threshold to fully realize the advantages of the invention.
  • Item 3 exemplifies a filament for which process conditions and properties are consistent, but with a single exception--in this case, the LPS is unexpectedly low.
  • a preferred group of filaments is of poly(ethylene terephthalate) having at least 93% dioxyethylene and terephthaloyl radicals, and especially at least 97% of such radicals, and having a relative viscosity of from about 9 to about 14, with a T 7 of greater than about 1.1 gpd, preferably greater than 1.2 gpd, a T+T 7 of greater than about 5 gpd and less than about 8 gpd, a dry heat shrinkage (196° C.) of less than about 10%, a "D" number of less than about 3.8 and greater than about 1.8, and a trimer "T" number of less than about 25.
  • the surface trimer content can generally be expected to be higher than for filaments of conventional viscosity.
  • Such dependence on the relative viscosity of the tensile properties (T+T 7 ) and of the surface trimer content ("T" number) is represented graphically as in FIG. 5. These relationships can also be represented mathematically, e.g.
  • steam-annealing according to the invention provides crimped annealed filaments having an improved balance of properties, this provides a way to improve somewhat the tensile strength of low molecular weight polymers, while improving the dyeability, and also providing filaments of lower flex resistance, i.e. improved pill-resistance, as shown in the following Example.

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  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
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US06/590,291 1983-05-04 1984-03-16 Process of making crimped, annealed polyester filaments Expired - Lifetime US4639347A (en)

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US06/590,291 US4639347A (en) 1983-05-04 1984-03-16 Process of making crimped, annealed polyester filaments
BR8402035A BR8402035A (pt) 1983-05-04 1984-04-30 Processo para fabricar filamentos recozidos ondulados;filamento ondulado de poli(tereftalato de etileno);feixe de filamentos
IN285/CAL/84A IN163524B (da) 1983-05-04 1984-04-30
IE1082/84A IE55981B1 (en) 1983-05-04 1984-05-02 Improved process for annealing polyester filaments and new products thereof
FI841725A FI80079C (fi) 1983-05-04 1984-05-02 Foerbaettrat kontinuerligt foerfarande foer vaermebehandling av polyesterfilament och daerigenom erhaollna nya produkter.
AU27577/84A AU578021B2 (en) 1983-05-04 1984-05-02 Improved annealed polyester filaments and a process for making them
CA000453503A CA1250414A (en) 1983-05-04 1984-05-03 Annealed polyester filaments and a process for making them
DK220884A DK220884A (da) 1983-05-04 1984-05-03 Fremgangsmaade til fremstilling af kontinuerlige fibre med forbedrede egenskaber
ES532133A ES532133A0 (es) 1983-05-04 1984-05-03 Un procedimiento para la manufactura de filamentos
NO841772A NO166336C (no) 1983-05-04 1984-05-03 Krusende polyesterfilamenter og fremgangsmaate ved fremstilling derav
AT84302988T ATE49243T1 (de) 1983-05-04 1984-05-03 Verfahren zur thermofixierung von polyesterfasern und so hergestellte fasern.
DE8484302988T DE3480941D1 (de) 1983-05-04 1984-05-03 Verfahren zur thermofixierung von polyesterfasern und so hergestellte fasern.
EP84302988A EP0125112B1 (en) 1983-05-04 1984-05-03 Improved process for annealing polyester filaments and new products thereof
GR74583A GR82071B (da) 1983-05-04 1984-05-03
TR3291/84A TR22997A (tr) 1983-05-04 1984-05-04 Poliester filamentlerin tavlanmasi icin islah edilmis usul ve bu usuluen yeni ueruenleri
PT78550A PT78550B (en) 1983-05-04 1984-05-04 Process for the manufacture of improved annealed polyester filaments
KR1019840002445A KR870001252B1 (ko) 1983-05-04 1984-05-04 어닐링된 폴리에스테르 필라멘트 및 이의 제조방법
MX201249A MX159169A (es) 1983-05-04 1984-05-04 Procedimiento para la manufactura de filamentos retorcidos y rizados de poliester
US06/942,714 US4704329A (en) 1984-03-16 1986-12-17 Annealed polyester filaments and a process for making them
IN215/CAL/88A IN168516B (da) 1983-05-04 1988-03-14
JP1230585A JPH02127536A (ja) 1983-05-04 1989-09-07 ポリエステルフイラメント
SG126/90A SG12690G (en) 1983-05-04 1990-02-22 Improved process for annealing polyester filaments and new products thereof
HK615/91A HK61591A (en) 1983-05-04 1991-08-08 Improved process for annealing polyester filaments and new products thereof

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IE (1) IE55981B1 (da)
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US4835053A (en) * 1987-11-24 1989-05-30 Basf Corporation Dark dyeing yarn containing polyester fibers and method of preparation
US4915926A (en) * 1988-02-22 1990-04-10 E. I. Dupont De Nemours And Company Balanced ultra-high modulus and high tensile strength carbon fibers
US5645936A (en) * 1986-01-30 1997-07-08 E. I. Du Pont De Nemours And Company Continuous filaments, yarns, and tows
US6168743B1 (en) 1999-06-15 2001-01-02 Arteva North America S.A.R.L. Method of continuously heat treating articles and apparatus therefor
US6458455B1 (en) 2000-09-12 2002-10-01 E. I. Du Pont De Nemours And Company Poly(trimethylene terephthalate) tetrachannel cross-section staple fiber
US6472066B1 (en) 2001-02-05 2002-10-29 Arteva North America S.A.R.L. Low shrinkage, uncrimped short-cut fibers for use in wet laid non-woven products and method for making same
US6752945B2 (en) 2000-09-12 2004-06-22 E. I. Du Pont De Nemours And Company Process for making poly(trimethylene terephthalate) staple fibers
US20060105094A1 (en) * 2004-11-16 2006-05-18 Nch Corporation Foaming food-grade lubricant
EP2169110A1 (de) 2008-09-25 2010-03-31 Trevira Gmbh Flammhemmende Hohlfaser mit silikonfreier Weichgriffausrüstung
EP2177651A1 (de) 2008-10-15 2010-04-21 Trevira Gmbh PTT-Faser mit verbesserter Einkräuselung
EP2660371A2 (en) * 2010-12-31 2013-11-06 Kolon Industries, Inc. Polyester fiber and method for manufacturing same
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same
WO2024146954A1 (en) 2023-01-08 2024-07-11 Indorama Ventures Public Company Limited Flame retardant copolymer with one or more non-virgin fossil components and methods of making the same

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TW503274B (en) 1998-02-04 2002-09-21 Hna Holdings Inc Calendering apparatus and method for heat setting a traveling multi-filament tow
DE10230964A1 (de) * 2002-07-10 2004-01-22 Neumag Gmbh & Co. Kg Verfahren und Vorrichtung zum Schmelzspinnen und Zerschneiden eines Spinnkabels
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Cited By (21)

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US5645936A (en) * 1986-01-30 1997-07-08 E. I. Du Pont De Nemours And Company Continuous filaments, yarns, and tows
US4833032A (en) * 1986-09-12 1989-05-23 E. I. Du Pont De Nemours And Company Texturing polyester yarns
US4835053A (en) * 1987-11-24 1989-05-30 Basf Corporation Dark dyeing yarn containing polyester fibers and method of preparation
US4915926A (en) * 1988-02-22 1990-04-10 E. I. Dupont De Nemours And Company Balanced ultra-high modulus and high tensile strength carbon fibers
US6168743B1 (en) 1999-06-15 2001-01-02 Arteva North America S.A.R.L. Method of continuously heat treating articles and apparatus therefor
DE10028709C2 (de) * 1999-06-15 2002-03-21 Arteva Tech Sarl Verfahren und Vorrichtung zur Wärmebehandlung von Fertigungsgegenständen
US6835339B2 (en) 2000-09-12 2004-12-28 E. I. Du Pont De Nemours And Company Process for preparing poly(trimethylene terephthalate) tetrachannel cross-section staple fiber
US20030071394A1 (en) * 2000-09-12 2003-04-17 Hernandez Ismael A. Process for preparing poly(trimethylene terephthalate) tetrachannel cross-section staple fiber
US6752945B2 (en) 2000-09-12 2004-06-22 E. I. Du Pont De Nemours And Company Process for making poly(trimethylene terephthalate) staple fibers
US6458455B1 (en) 2000-09-12 2002-10-01 E. I. Du Pont De Nemours And Company Poly(trimethylene terephthalate) tetrachannel cross-section staple fiber
US6872352B2 (en) 2000-09-12 2005-03-29 E. I. Du Pont De Nemours And Company Process of making web or fiberfill from polytrimethylene terephthalate staple fibers
US6472066B1 (en) 2001-02-05 2002-10-29 Arteva North America S.A.R.L. Low shrinkage, uncrimped short-cut fibers for use in wet laid non-woven products and method for making same
US20060105094A1 (en) * 2004-11-16 2006-05-18 Nch Corporation Foaming food-grade lubricant
EP2169110A1 (de) 2008-09-25 2010-03-31 Trevira Gmbh Flammhemmende Hohlfaser mit silikonfreier Weichgriffausrüstung
EP2177651A1 (de) 2008-10-15 2010-04-21 Trevira Gmbh PTT-Faser mit verbesserter Einkräuselung
DE102008051738A1 (de) 2008-10-15 2010-04-22 Trevira Gmbh PTT-Faser mit verbesserter Einkräuselung
EP2660371A2 (en) * 2010-12-31 2013-11-06 Kolon Industries, Inc. Polyester fiber and method for manufacturing same
EP2660371A4 (en) * 2010-12-31 2014-05-21 Kolon Inc POLYESTER FIBER AND MANUFACTURING METHOD THEREFOR
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same
US10589474B2 (en) 2011-01-12 2020-03-17 Compagnie Chomarat Methods for manufacturing sublaminate modules and forming composite laminated structures from the same
WO2024146954A1 (en) 2023-01-08 2024-07-11 Indorama Ventures Public Company Limited Flame retardant copolymer with one or more non-virgin fossil components and methods of making the same

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PT78550A (en) 1984-06-01
MX159169A (es) 1989-04-26
GR82071B (da) 1984-12-13
TR22997A (tr) 1989-01-06
PT78550B (en) 1986-07-14
KR870001252B1 (ko) 1987-06-29
JPH02127536A (ja) 1990-05-16
IE55981B1 (en) 1991-03-13
EP0125112A3 (en) 1986-08-27
EP0125112B1 (en) 1990-01-03
CA1250414A (en) 1989-02-28
NO166336C (no) 1991-07-03
DE3480941D1 (de) 1990-02-08
EP0125112A2 (en) 1984-11-14
NO166336B (no) 1991-03-25
DK220884D0 (da) 1984-05-03
FI80079B (fi) 1989-12-29
FI841725A (fi) 1984-11-05
KR850002490A (ko) 1985-05-13
FI80079C (fi) 1990-04-10
ES8600793A1 (es) 1985-10-16
IN163524B (da) 1988-10-08
DK220884A (da) 1984-11-05
BR8402035A (pt) 1984-12-11
NO841772L (no) 1984-11-05
HK61591A (en) 1991-08-16
IE841082L (en) 1984-11-04
ES532133A0 (es) 1985-10-16
SG12690G (en) 1990-10-26

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